Metal organic structure

Abstract

To provide a metal organic structure having excellent desorbing performance of an adsorbed substance.SOLUTION: Provided is a metal organic structure constituted of organic ligand and metal ion, where a half-value width of a peak having the largest peak intensity out of a diffraction spectrum within the range of 2θ=3 to 40° which is obtained by X-ray diffraction measurement is 0.05 to 0.225°, and a glass deposit rate calculated by the following measuring method is 0 to 20 mass %. [Measurement of a glass deposit rate] when 100 mg of a sample of the metal organic structure is input from a top end of a vertically erected glass tube having a diameter 6 mm and a length 200 mm, a mass ratio of a sample deposited inside the glass tube to the input sample is a glass deposit rate.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a metal-organic framework. [Background technology]

[0002] Metal organic frameworks, also known as porous coordination polymers, are a type of material that forms a porous structure through coordination bonds between metal ions and organic ligands. They are expected to be used for gas adsorption / desorption, as well as in catalysts, etc.

[0003] For example, Patent Document 1 discloses a metal organic framework obtained by supplying a solid mixture containing a metal salt and a multidentate organic ligand, kneading or grinding the mixture for a time sufficient to produce a powdered precursor of a metal organic framework, and further heating the powdered precursor for a time and at a temperature sufficient to convert the powdered precursor into the metal organic framework. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] WO2020 / 159631 Summary of the Invention [Problem to be solved by the invention]

[0005] Metal-organic frameworks can be regenerated and reused by adsorbing substances such as water, carbon dioxide, and hydrogen, and then heating them to a specified temperature to desorb the adsorbed substances from the MOF. However, it is desirable to be able to desorb the adsorbed substances efficiently in this process.

[0006] The above-mentioned Patent Document 1 describes the powder form of the obtained metal organic framework and the difference in crystallinity from the precursor, but does not consider at all the desorption characteristics of the adsorbed substance.

[0007] Therefore, an object of the present invention is to provide a metal organic framework that is excellent in the desorption performance of adsorbed substances. [Means for solving the problem]

[0008] The present invention, which has achieved the above object, is as follows. [1] A metal organic framework composed of an organic ligand and a metal ion, A metal organic framework having a half-width of the peak with the highest peak intensity of 0.05 to 0.225° in a diffraction spectrum in the range of 2θ=3 to 40° obtained by X-ray diffraction measurement, and a glass adhesion ratio of 0 to 20 mass% calculated by the following measurement method. [Measurement of glass adhesion rate] When 100 mg of a metal-organic framework sample is poured into the top end of a vertically standing glass tube with a diameter of 6 mm and a length of 200 mm, the mass ratio of the sample that adheres to the inside of the glass tube to the sample poured in is defined as the glass adhesion rate. [2] The organic ligand is an oxalate ion (COO - )2 and R(COO - ) n (R is an n-valent group, n is an integer of 2 or more). [3] The metal organic framework according to [1] or [2], wherein the metal ion comprises at least one metal ion selected from elements in periods 3 to 6 and groups 2 to 14 of the periodic table. Effect of the Invention

[0009] According to the present invention, the half-width of the peak with the greatest peak intensity obtained by X-ray diffraction measurement and the glass adhesion rate calculated by a specified measurement method are appropriately adjusted, so that the adsorbed substances can be efficiently desorbed. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] (1) Metal-organic framework The metal organic framework of the present invention is a metal organic framework composed of an organic ligand and a metal ion, and has a half-width of a peak with the highest peak intensity of a diffraction spectrum in the range of 2θ=3 to 40° obtained by X-ray diffraction measurement of 0.05 to 0.225°, and a glass adhesion ratio of 0 to 20 mass% calculated by the following measurement method. [Measurement of glass adhesion rate] When 100 mg of a metal-organic framework sample is poured into the top end of a vertically standing glass tube with a diameter of 6 mm and a length of 200 mm, the mass ratio of the sample that adheres to the inside of the glass tube to the sample poured in is defined as the glass adhesion rate.

[0011] (1-1)Organic ligand In organic ligands, the functional group X that can coordinate to a metal ion is COOH, a carboxylic anhydride group, -OH, -OR 11 , -NH2, -NHR 11 , -N(R 11 )2, -CN, a halogeno group, -C(=S)SH, -C(=O)SH and tautomers thereof, -SO3H, -SS-, etc. (see above R 11 Each of the groups represents an alkyl group having 1 or 2 carbon atoms. It is preferable that the organic ligand is a polydentate ligand and contains COOH as the functional group X. More specifically, the oxalate ion (COO - )2 and R(COO - ) n (R is an n-valent group, n is an integer of 2 or more).

[0012] The R is preferably an aliphatic chain hydrocarbon group, an aliphatic cyclic hydrocarbon group, an aliphatic heterocyclic hydrocarbon group (a group in which one or more carbon atoms of an aliphatic cyclic hydrocarbon group are replaced with heteroatoms), an aromatic hydrocarbon group, or an aromatic heterocyclic hydrocarbon group (a group in which one or more carbon atoms of an aromatic hydrocarbon group are replaced with heteroatoms). The aliphatic chain hydrocarbon group may be linear or branched, and may be a saturated or unsaturated hydrocarbon group. The heteroatom in the aliphatic heterocyclic hydrocarbon group or aromatic heterocyclic hydrocarbon group is preferably nitrogen. n is preferably 2 or more and 4 or less, more preferably 2 or more and 3 or less, and most preferably 3.

[0013] The above-mentioned aliphatic chain hydrocarbon group, aliphatic cyclic hydrocarbon group, aliphatic heterocyclic hydrocarbon group, aromatic hydrocarbon group and aromatic heterocyclic hydrocarbon group may further include a carboxylic anhydride group, -OH, -OR 12 , -NH2, -NHR 12 , -N(R 12 The R may contain one or more functional groups Y selected from the group consisting of -CN, a halogeno group, -C(=S)SH, -C(=O)SH and tautomers thereof, -SO3H, and -SS-. 12 Each of these represents an alkyl group having 1 or 2 carbon atoms.

[0014] Examples of the aromatic heterocyclic hydrocarbon group include pyrrole, pyrazole, imidazole, thiazole, oxazole, pyridine, pyrimidine, pyridazine, pyrazine, and triazine.

[0015] The above R is an aromatic hydrocarbon group, and is preferably a group which may have the above-mentioned functional group Y, and is preferably an aromatic hydrocarbon group which does not have the functional group Y.

[0016] The number of carbon atoms in R is preferably 3 or more, more preferably 6 or more, and is preferably 30 or less, more preferably 24 or less, even more preferably 18 or less, even more preferably 12 or less, and most preferably 10 or less.

[0017] The organic ligand preferably includes a dicarboxylic acid having two protons removed from two carboxyl groups (-COOH) or a tricarboxylic acid having three protons removed from three carboxyl groups, and more preferably includes a tricarboxylic acid having three protons removed from three carboxyl groups.

[0018] The dicarboxylic acids include oxalic acid, succinic acid, fumaric acid, tartaric acid, 1,4-butanedicarboxylic acid, 1,4-butenedicarboxylic acid, 4-oxopyran-2,6-dicarboxylic acid, 1,6-hexanedicarboxylic acid, decanedicarboxylic acid, 1,8-heptadecanedicarboxylic acid, 1,9-heptadecanedicarboxylic acid, heptadecanedicarboxylic acid, acetylenedicarboxylic acid, 1,2-benzenedicarboxylic acid (phthalic acid), 1,3-benzenedicarboxylic acid (isophthalic acid), 2,3-pyridinedicarboxylic acid, 1,3-butadiene-1,4-dicarboxylic acid, 1,4 -Benzene dicarboxylic acid (terephthalic acid), 2-aminoterephthalic acid, 2,5-dihydroxyterephthalic acid, imidazole-2,4-dicarboxylic acid, 3,5-pyrazole dicarboxylic acid, 2-methylquinoline-3,4-dicarboxylic acid, quinoline-2,4-dicarboxylic acid, quinoxaline-2,3-dicarboxylic acid, 6-chloroquinoxaline-2,3-dicarboxylic acid, 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid, quinoline-3,4-dicarboxylic acid, 7-chloro-4-hydroxyquinoline-2,8-dicarboxylic acid, diimide dicarboxylic acid, pyridinium 2,6-dicarboxylic acid, 2-methylimidazole-4,5-dicarboxylic acid, thiophene-3,4-dicarboxylic acid, thiophene-2,5-dicarboxylic acid, 2,2'-dithiodibenzoic acid, 2-isopropylimidazole-4,5-dicarboxylic acid, tetrahydropyran-4,4-dicarboxylic acid, perylene-3,9-dicarboxylic acid, perylenedicarboxylic acid, Pluriol E200-dicarboxylic acid, 3,6-dioxaoctanedicarboxylic acid, 3,5-cyclohexadiene-1,2-dicarboxylic acid, octanedicarboxylic acid, pentane-3,3-carboxylic acid, 4,4' -Dihydroxybiphenyl-3,3'-dicarboxylic acid, 4,4'-diamino-1,1'-biphenyl-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, benzidine-3,3'-dicarboxylic acid, 1,4-bis(phenylamino)benzene-2,5-dicarboxylic acid, 1,1'-binaphthyl dicarboxylic acid, 7-chloro-8-methylquinoline-2,3-dicarboxylic acid, 1-anilinoanthraquinone-2,4'-dicarboxylic acid, polytetrahydrofuran 250-dicarboxylic acid, 1,4-bis(carboxymethyl)piperazine-2,3-dicarboxylic acid, 7-chloroquinoline-3,8-dicarboxylic acid, 1-(4-carboxy)phenyl-3-(4-chloro)phenylpyrazoline-4,5-dicarboxylic acid, 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid, phenylindanedicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, naphthalene-1,8-dicarboxylic acid, 2-benzoylbenzene-1,3-dicarboxylic acid, 1,3-dibenzyl-2-oxoimidazolidine-4,5-dicarboxylic acid, ,5-cis-dicarboxylic acid, 2,2'-biquinoline-4,4'-dicarboxylic acid, pyridine-3,4-dicarboxylic acid, 3,6,9-trioxaundecanedicarboxylic acid, hydroxybenzophenonedicarboxylic acid, Pluriol E300-dicarboxylic acid, Pluriol E400-dicarboxylic acid, Pluriol E600-dicarboxylic acid, pyrazole-3,4-dicarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5,6-dimethyl-2,3-pyrazinedicarboxylic acid, bis(4-aminophenyl)etherdiimide-dicarboxylic acid, 4,4'-diaminodiphenyl bis(4-aminophenyl)sulfonediimide-dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 8-methoxy-2,3-naphthalenedicarboxylic acid, 8-nitro-2,3-naphthalenedicarboxylic acid, 8-sulfo-2,3-naphthalenedicarboxylic acid, anthracene-2,3-dicarboxylic acid, 2',3'-diphenyl-p-terphenyl-4,4''-dicarboxylic acid, (di Phenyl ether)-4,4'-dicarboxylic acid, imidazole-4,5-dicarboxylic acid, 4(1H)-oxothiochromene-2,8-dicarboxylic acid, 5-tert-butyl-1,3-benzenedicarboxylic acid, 7,8-quinolinedicarboxylic acid, 4,5-imidazoledicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, hexatriacontanedicarboxylic acid, tetradecanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 5-hydroxy-1,3-benzenedicarboxylic acid, 2,5-dihydroxy-1,4-benzenedicarboxylic acid, pyrazine-2,3-dicarboxylic acid, furan-2,5-dicarboxylic acid, 1-nonene-6,9-dicarboxylic acid, eicosene dicarboxylic acid, 4,4'-dihydroxy-diphenylmethane-3,3'-dicarboxylic acid, 1-amino-4-methyl-9,10-dioxo-9,10-dihydroanthracene-2,3-dicarboxylic acid, 2,5-pyridinedicarboxylic acid, cyclohexene-2,3-dicarboxylic acid, 2,9-dichlorofluorbin-4,11-dicarboxylic acid, 7-chloro-3-methylquinoline-6,8-dicarboxylic acid, 2,4-dichlorobenzophenone-2',5'-dicarboxylic acid, 1,3-benzenedicarboxylic acid Examples of the carboxylic acid include 2,6-pyridinedicarboxylic acid, 1H-pyrrole-2,5-dicarboxylic acid, 1-methylpyrrole-3,4-dicarboxylic acid, 1-benzyl-1H-pyrrole-3,4-dicarboxylic acid, anthraquinone-1,5-dicarboxylic acid, 3,5-pyrazole dicarboxylic acid, 2-nitrobenzene-1,4-dicarboxylic acid, heptane-1,7-dicarboxylic acid, cyclobutane-1,1-dicarboxylic acid, 1,14-tetradecane dicarboxylic acid, 5,6-dehydronorbornane-2,3-dicarboxylic acid, 5-ethyl-2,3-pyridinedicarboxylic acid, and camphor dicarboxylic acid.

[0019] Examples of tricarboxylic acids include tricarballylic acid, aconitic acid, trimellitic acid, trimesic acid (1,3,5-benzene tricarboxylate), biphenyl-3,4',5-tricarboxylic acid, and 1,3,5-tris(4-carboxyphenyl)benzene, with 1,3,5-benzene tricarboxylate being particularly preferred.

[0020] The organic ligand may further include other organic ligands in addition to one or more selected from the group L1, and examples thereof include at least one selected from the group L2 consisting of urea, pyrazine, oxazole, isoxazole, thiazole, imidazole, pyrazole, 1,2,3-thiadiazole, pyridazine, pyrimidine, purine, pteridine, 2,2'-bipyridine, and 4,4'-bipyridine.

[0021] (1-2) Metal ions The metal ions preferably include at least one metal ion selected from elements in periods 3 to 6 and groups 2 to 14 of the periodic table, more preferably at least one metal selected from the group consisting of Mg, Al, Ga, In, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr and Hf, still more preferably at least one metal ion selected from the group consisting of Cu, Al, Ti, V, Fe, Co, Ni and Zr, and particularly preferably Cu ions. In this specification, the term "metal" is used to include semimetals such as Si and Ge.

[0022] The molar ratio P of the organic ligand to the metal ion (organic ligand / metal ion) is preferably 5 times or less the theoretical molar ratio P0 (organic ligand / metal ion) at which the metal ion and the organic ligand are bonded to be electrically neutral, i.e., P / P0 is preferably 5 or less, more preferably 3 or less, further preferably 2 or less, and is preferably 0.8 or more.

[0023] More specifically, the molar ratio of the organic ligand to the metal ion (organic ligand / metal ion) is preferably less than 3, and by setting it in such a range, the metal ion and the organic ligand can be mixed uniformly. The molar ratio is more preferably 2.5 or less, even more preferably 2 or less, and even more preferably 1.5 or less, and is preferably 0.1 or more, more preferably 0.2 or more, and even more preferably 0.3 or more.

[0024] The molar ratio of organic ligand / metal ion can be adjusted by adjusting the ratio of the amount of metal ion in an ionic metal compound used in the production method described below to the amount of an organic compound capable of forming a coordinate bond with the metal ion.

[0025] (1-3) Half-width In the diffraction spectrum in the range of 2θ=3 to 40° obtained by X-ray diffraction measurement of the metal organic framework of the present invention, the half-width of the peak with the highest peak intensity is 0.05 to 0.225°. When the half-width is in the above range, the crystallinity of the metal organic framework is good. The half-width is preferably 0.21° or less, more preferably 0.20° or less, and even more preferably 0.17° or less.

[0026] (1-4) Glass adhesion rate The glass adhesion rate is measured as follows. [Measurement of glass adhesion rate] When 100 mg of a metal-organic framework sample is poured into the top end of a vertically standing glass tube with a diameter of 6 mm and a length of 200 mm, the mass ratio of the sample that adheres to the inside of the glass tube to the sample poured in is defined as the glass adhesion rate.

[0027] It is preferable to use borosilicate glass as the glass tube. Specifically, the 3-1594-03 manufactured by AS ONE Corporation used in the examples can be cut to a length of 200 mm and used.

[0028] The temperature when measuring the glass adhesion rate is preferably 15 to 40° C., and the relative humidity is preferably 20 to 80%.

[0029] When the glass adhesion rate is 0 to 20 mass% and the half width is 0.05 to 0.225°, the substance once adsorbed by the metal-organic framework can be efficiently desorbed. Furthermore, when the glass adhesion rate is within the above range, the effect of excellent handleability during recovery from the production facility, transportation, storage, etc. is also achieved. The glass adhesion rate is preferably 15 mass% or less, more preferably 10 mass% or less, and even more preferably 7 mass% or less, and the lower limit is not particularly limited, but may be 1 mass%.

[0030] (1-5) Desorption performance When the glass adhesion rate is 0 to 20 mass% and the half width is 0.05 to 0.225°, the metal-organic framework can efficiently desorb substances once adsorbed thereon. More specifically, the amount of desorbed water measured according to the examples described later can be 8.5 mass% or more, more preferably 9 mass% or more, and even more preferably 11 mass% or more. The upper limit is not particularly limited, but may be, for example, 20 mass%.

[0031] (2) Method for manufacturing metal-organic structures The metal organic framework of the present invention can be obtained by extruding a mixture of an ionic metal compound and an organic compound capable of forming a coordinate bond with a metal ion. The counter anion of the ionic metal compound is OH. - It is important that the extrusion process is carried out in the absence of solvent and base at a temperature of 60° C. or higher.

[0032] (2-1) Organic compounds capable of forming coordinate bonds with metal ions The organic compound capable of forming a coordinate bond with a metal ion is an organic compound that becomes an organic ligand in a metal organic framework. Therefore, all of the explanations regarding the organic ligand in (1-1) above can be referred to. The organic compound capable of forming a coordinate bond with a metal ion is an organic compound that becomes the group L1 in a metal organic framework, that is, oxalic acid and R(COOH) n (R is an n-valent group, n is an integer of 2 or more). The organic compound preferably contains a dicarboxylic acid or a tricarboxylic acid, and more preferably contains a tricarboxylic acid. For details of R, n, dicarboxylic acid, and tricarboxylic acid, see the explanation in (1-1) above.

[0033] (2-2) Ionic metal compounds The ionic metal compound is a compound of a metal ion in a metal organic framework and a counter anion, and the counter anion is OH -In other words, the ionic metal compound used in the present invention has a counter anion other than OH. - The counter anion in ionic metal compounds is NO3 - , SO4 2- , CH3COO - , Cl - , Br - , and (OR 2 ) - (R 2 is preferably at least one selected from NO3 - is particularly preferred.

[0034] The metal ions in the ionic metal compound are the same as those described in (1-2) above.

[0035] The ionic metal compound contains at least one metal selected from the elements in the third to sixth periods and the second to fourth groups of the periodic table (preferably Cu, Al, Ti, V, Fe, Co, Ni, and Zr), and the counter anion is NO3 - , SO4 2- , CH3COO - , Cl - , Br - , and (OR 2 ) - (R 2 is an organic group) (preferably NO3 - ) is more preferred.

[0036] In addition to compound M1, the ionic metal compound may further include compound M2 which is at least one of an alkali metal hydroxide and an alkali metal azide.

[0037] (2-3) Extrusion processing The extrusion process is usually carried out by feeding a mixture of the organic compound and the ionic metal compound (hereinafter sometimes referred to as a raw material mixture) into a barrel equipped with a screw and rotating the screw. The screw may be a single screw or a multi-screw having two or more screws. In the present invention, the extrusion process is carried out at a temperature of 60°C or higher in the absence of a solvent and a base. That is, no solvent or base is used from the start to the end of the extrusion process, and of course the raw material mixture does not contain a solvent or a base when it is fed into the extruder. In addition, it is sufficient that the temperature is 60°C or higher at any stage from the start to the end of the extrusion process, and it is preferable that the temperature is 60°C or higher for at least 2 / 3 of the time required from the start to the end of the extrusion process.

[0038] "No solvent and no base" means that the amount of the solvent is 0.1 part by mass or less (preferably 0.005 part by mass or less, more preferably 0 part by mass) and the amount of the base is 0.1 part by mass or less (preferably 0.005 part by mass or less, more preferably 0 part by mass) per 100 parts by mass of the raw material mixture.

[0039] The solvent is not limited to substances added with the intention of acting as a solvent, but includes any liquid including water or an organic solvent. Although a base can effectively act to increase the reactivity between the organic compound and the ionic metal compound, it is not used in the present invention. Examples of the base include NaOH, KOH, and LiOH.

[0040] The temperature at which the extrusion process is carried out is preferably 70° C. or higher, more preferably 90° C. or higher, and even more preferably 100° C. or higher, and is preferably lower than 200° C., and more preferably 190° C. or lower.

[0041] In addition, it is preferable to use an organic compound and an ionic metal compound capable of forming a coordinate bond with a metal ion to be subjected to extrusion processing that have not been subjected to a pulverization treatment using a vibrating ball mill or the like.

[0042] The extruder used for extrusion processing includes, for example, a barrel equipped with a screw, a raw material supply section that supplies a raw material or a raw material mixture to the barrel, and a discharge section that discharges the reactant after extrusion processing. The screw may be a single screw or a multi-shaft screw having two or more shafts, and is preferably a twin-shaft screw. In the case of a multi-shaft screw having two or more shafts, the multiple screws may rotate in the same direction, or at least one screw may rotate in the opposite direction to the remaining screws, but it is preferable that the multiple screws rotate in the same direction.

[0043] The screw preferably has a shaft portion extending in one direction and a blade portion formed in a spiral shape around the shaft portion, and can rotate around the axis of the shaft portion. The rotation speed of the screw is, for example, 5 to 50 rpm, and preferably 10 to 30 rpm. The ratio (L / D) of the length L of the screw to the diameter D including the blade portion is preferably 15 to 40, and more preferably 20 to 35. The diameter D of the screw including the blade portion is, for example, 10 to 20 mm.

[0044] The barrel may be configured such that a plurality of sections capable of individually controlling the temperature are connected in the axial direction of the screw.

[0045] The discharge section for discharging the reaction product after extrusion is preferably provided with one or more nozzles, and the nozzle diameter is preferably 0.5 to 3 mm.

[0046] When feeding an organic compound capable of forming a coordinate bond with a metal ion and an ionic metal compound into an extruder, the organic compound and the ionic metal compound may be mixed in advance and then fed into the extruder, or they may be fed into the extruder simultaneously, but it is preferable to mix them in advance in order to efficiently proceed with the reaction.

[0047] In addition to the raw material supply section, a side feed may be provided on the discharge section side along the axis of the screw relative to the raw material supply section. In an embodiment in which the extrusion processing machine is equipped with a side feed, one of the organic compound capable of forming a coordinate bond with a metal ion and the ionic metal compound may be fed from the raw material supply section, and the other may be fed from the side feed. In this way, after the raw material fed from the raw material supply section has progressed in melting, it can be mixed with the raw material fed from the side feed, thereby increasing the reaction efficiency. It is also preferable to provide a local exhaust device at the side feed, which makes it possible to recover gases and the like resulting from decomposition of the raw materials and impurities, thereby ensuring the safety of the operation. Furthermore, pellets containing MOFs may be produced by feeding synthetic resin, which is the raw material for chemical fibers, from a side feed, and then the pellets may be processed into fibers to produce MOF-containing fibers. Examples of such synthetic resins include polyolefin-based resins, polyester-based resins, and polyamide-based resins.

[0048] Moreover, the production method of the present invention preferably does not include a step of treating the raw materials, the raw material mixture, or the reactants after the extrusion process at 200° C. or higher, including before, during, and after the extrusion process. EXAMPLES

[0049] The present invention will be described in more detail below with reference to examples. The present invention is not limited to the following examples, and can of course be modified within the scope of the above and below-mentioned aims, and all such modifications are within the technical scope of the present invention.

[0050] Examples 1 to 3 A mixture of 63 g of copper (II) nitrate trihydrate (Cu(NO3)2·3H2O, manufactured by Tokyo Chemical Industry Co., Ltd.) and 37 g of 1,3,5-benzenetricarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was fed into the raw material inlet of a twin-screw extruder, and the reaction product was obtained from a nozzle attached to the discharge section. The barrel of the extruder is composed of the raw material inlet, kneading section 1, side feed section, and kneading section 2, which are connected in order from the raw material inlet to the discharge section, and each section can be individually temperature-controlled. The internal volume of the barrel is about 100 ml. The temperature conditions at each section and the screw rotation speed are as shown in Table 1 below. The nozzle diameter of the nozzle attached to the discharge section is 2 mm, and the reaction product obtained by extrusion processing was then washed three times with 50 mL of methanol and dried under reduced pressure at 100 °C for 24 hours.

[0051] Comparative Example 1 Solution A was prepared by dissolving 1.765 g of copper(II) nitrate trihydrate (Cu(NO3)2·3H2O, manufactured by Tokyo Chemical Industry Co., Ltd.) in 24.4 g of ion-exchanged water, and solution B was prepared by dissolving 0.86 g of 1,3,5-benzenetricarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) in 19.2 g of ethanol, and mixed at room temperature and allowed to stand for 12 hours at 120°C for maturation. The resulting precipitated solid was washed with 100 ml of ethanol, and the resulting filter cake was dried in a vacuum drying oven at 40°C for 11 hours to obtain 1.02 g of the product.

[0052] Comparative Example 2 A solution of 0.2 g of copper hydroxide (Tokyo Chemical Industry Co., Ltd., Cu(OH)2) and 0.28 g of 1,3,5-benzenetricarboxylic acid (Tokyo Chemical Industry Co., Ltd.) dissolved in 0.28 g of methanol was placed in a 20 ml ball mill container made of zeolite together with 10 zeolite balls (φ: 10 mm) and mixed at room temperature at 400 rpm. The treatment in the ball mill was performed after every 5 minutes of rotation with a 5 minute interval, for a total of 30 5 minute rotations. The product was then scraped up with a spatula and collected, and dried in a vacuum drying oven at 40°C for 11 hours, yielding 0.39 g of product.

[0053] Comparative Example 3 A mixture of 42 g of copper hydroxide (Cu(OH)2), 58 g of 1,3,5-benzenetricarboxylic acid, and 58 g of methanol was fed to the raw material inlet of a twin-screw extruder similar to that used in Examples 1 to 3, and a reaction product was obtained from the nozzle. The temperature conditions at each point and the screw rotation speed are shown in Table 1 below. The reaction product obtained by extrusion was then washed three times with 50 mL of methanol and dried under reduced pressure at 100°C for 24 hours.

[0054] [Table 1]

[0055] The metal organic frameworks obtained in the examples and comparative examples were evaluated by the following methods.

[0056] (1) Measurement of the half-width of the peak with the highest peak intensity X-ray diffraction measurements were performed using an X-ray diffractometer SmartLab manufactured by Rigaku Corporation under the following conditions. Source:Cu Measurement range: 2θ=3~40° Step size: 0.01° Scanning speed: 3° / min Measurement temperature: room temperature (25℃) Within the above 2θ range, the position of the peak with the highest peak intensity was found, and the angle at half the intensity of the peak was measured and defined as the half-width. If the peak with the highest peak intensity overlaps with an adjacent peak and has an asymmetric shape, the 2θ of the point showing half the intensity of the peak on the non-overlapping side is subtracted from the 2θ of the point with the highest peak intensity, and the half-width is calculated by multiplying this value by two.

[0057] (2) Measurement of glass adhesion rate (i) Cut the required number of commercially available glass tubes (φ6 mm × 1500 mm, AS ONE 3-1594-03 Glass Tube φ6 Standard Tube (STD)) into 200 mm lengths using a glass cutter such as an ampoule cutter. (ii) Make a funnel using medicine paper and tape. (iii) Prepare a paper wrapper for weighing the sample, and weigh the paper wrapper and the funnel prepared in (ii) above. (iv) Approximately 100 mg of the sample is weighed into the drug packaging paper. (v) Prepare an empty sample bottle in which to collect the sample after measuring the glass adhesion rate, and weigh it. (vi) Stand the 200 mm glass tube vertically and place the funnel on top and the sample bottle on the bottom, leaving a gap of about 10 mm between the bottom of the sample bottle and the lower end of the glass tube. (vii) Drop the sample from the paper into the funnel and pass the sample through the glass tube. (viii) Remove the glass tube through which the sample has passed without vibrating it. (ix) The sample that passes through the glass tube is collected in the sample bottle at the bottom, and the weights of the wrapping paper, funnel, and sample bottle containing the sample are each measured after the test. (x) The glass adhesion rate is the ratio of the weight of the sample that adheres to the inside of the glass tube to the weight of the sample that is supplied from the wrapping paper through the funnel into the glass tube.

[0058] (3) Desorption performance test Using a Rigaku Thermogravimetry-Differential Thermal Analysis (TG-DTA) device, the amount of moisture desorbed from the metal-organic framework pretreated under the following conditions was measured. Pretreatment conditions: 12 hours in an air atmosphere conditioned at 25°C and a relative pressure of 0.5 Amount of desorption: After the above pretreatment, the temperature was increased at a rate of 5°C / min under nitrogen flow and held at 50°C for 30 minutes. The weight loss W during this period (25 to 50°C) was 25-50 Measure this W 25-50 was divided by the weight of the sample after the pretreatment to obtain the amount of desorption (mass %).

[0059] The results of (1) to (3) above are shown in Table 2.

[0060] [Table 2] [Industrial Applicability]

[0061] The metal-organic framework of the present invention is useful because it is suitable for adsorption and removal of gases and organic molecules. Examples of the gases include carbon dioxide, hydrogen, carbon monoxide, oxygen, nitrogen, hydrocarbons having 1 to 4 carbon atoms, rare gases, hydrogen sulfide, ammonia, sulfur oxides, nitrogen oxides, and siloxanes. Examples of the organic molecules include hydrocarbons having 5 to 8 carbon atoms, alcohols having 1 to 8 carbon atoms, aldehydes having 1 to 8 carbon atoms, carboxylic acids having 1 to 8 carbon atoms, ketones having 1 to 8 carbon atoms, amines having 1 to 8 carbon atoms, esters having 1 to 8 carbon atoms, and amides having 1 to 8 carbon atoms. The organic molecules may contain an aromatic ring.

Claims

1. A metal organic framework composed of organic ligands and metal ions, A metal organic framework having a diffraction spectrum obtained by X-ray diffraction measurement in the range of 2θ=3 to 40°, in which the half width of the peak with the greatest peak intensity is 0.05 to 0.21°, and a glass adhesion rate calculated by the following measurement method is 0 to 20 mass%. [Measurement of glass adhesion rate] When 100 mg of a metal-organic framework sample is poured into the top end of a vertically standing glass tube having a diameter of 6 mm and a length of 200 mm, the mass ratio of the sample that adheres to the inside of the glass tube relative to the poured sample is defined as the glass adhesion rate.

2. A metal-organic framework comprising organic ligands and metal ions, obtained by extruding a mixture of an ionic metal compound and an organic compound capable of forming a coordinate bond with a metal ion, the counter anion of the ionic metal compound is an anion other than OH − ; The metal-organic framework, wherein the extrusion processing is carried out in the absence of a solvent and a base at a temperature of 60°C or higher.

3. The metal organic structure according to claim 2, wherein the molar ratio of the organic compound to the metal ions in the ionic metal compound (organic compound / metal ions) is 0.3 to 1.

5.

4. The organic ligand is an oxalate ion (COO － ) ２ and R(COO － ) ｎ 2. The metal organic structure according to claim 1, comprising at least one selected from the group consisting of carboxylates represented by the following formula: (R is an n-valent group, and n is an integer of 2 or more).

5. 2. The metal organic structure according to claim 1, wherein the metal ions comprise at least one metal ion selected from elements in periods 3 to 6 and groups 2 to 14 of the periodic table.

6. The metal organic structure according to claim 1, wherein the organic ligand comprises at least one selected from R(COO − ) 3 (wherein R is an aromatic hydrocarbon group having no functional group and R is an aromatic hydrocarbon group having 6 to 10 carbon atoms), and the metal ion comprises at least one metal ion selected from the group consisting of Cu, Al, Ti, V, Fe, Co, Ni, and Zr.